Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
  • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
  • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D341/00—Heterocyclic compounds containing rings having three or more sulfur atoms as the only ring hetero atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
  • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
  • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/35—Non-linear optics
  • G02F1/355—Non-linear optics characterised by the materials used
  • G02F1/361—Organic materials
  • G02F1/3613—Organic materials containing Sulfur
  • G02F1/3614—Heterocycles having S as heteroatom

Definitions

• the present invention relates to new metal complexes of thiacalix [4] arene derivatives, in particular with a transition metal, as well as their use, in particular for the manufacture of materials having optical limiter properties.
• Y is a bivalent bridging group at least one of said bridging groups being a sulfur atom
• R ' is hydrogen, a hydrocarbyl group or a hetero-substituted hydrocarbyl group and n is an integer at least equal to 4.
• thiacalix [4] arene derivatives of formula (B): wherein R ' 5 represents a hydrogen atom or a tert-butyl group and R' 7 represents a methyl, ethyl, n-propyl or rc-butyl group.
• One of the objectives which the invention proposes to achieve is to develop new thiacalix [4] arene derivatives having in particular the following properties
• thermochromic properties Certain thiacalix [4] arene complexes according to the invention with a transition metal have thermochromic properties.
• R 2a> 3a and R 4a identical or different, each independently represent:
• Ri represents a phenyl, benzyl or naphthyl group, unsubstituted or substituted one or more times by a halogen atom, a (C ⁇ -C 4 ) alkyl group, (C ⁇ - C 4 ) alkenyl or (C ⁇ -C 4 ) alkynyl, or else,
• R, R and R 4 each independently represent a (C ⁇ -C 4 ) alkyl group
• a phenylazo group optionally substituted preferably in position 4 by a nitro group
• a group -N CHR 5 in which R 5 represents a (C ⁇ -C) alkyl, pyridyl or phenyl group,
• R 6 represents a hydrogen atom, a group (C ⁇ -C 4 ) alkyl, tri (Cj-C 4 ) alkylsilyl, phenyl, or a group of formula: where R 6 'represents a hydrogen atom or a phenyl optionally substituted in para by a (C ⁇ -C 6 ) alkyl group,
• alkyl is meant a monovalent hydrocarbon radical, linear or branched, saturated.
• alkenyl is meant a monovalent hydrocarbon radical, linear or branched, unsaturated comprising a double bond.
• alkynyl is meant a monovalent hydrocarbon, linear or branched unsaturated radical comprising a triple bond.
• (C ⁇ -C 4 ) alkyl means an alkyl radical comprising from 1 to 4 carbon atoms.
• halogen atom is meant a chlorine, bromine, iodine or fluorine atom. It will be noted that the exclusion introduced into the definition of the compounds of formula (I) is in particular intended to exclude the compounds already described in the prior art, namely in the publications Tetrahedron Letters 1998, 39, 8915-8918 and 2000 , 41, 9339-9344.
• the present invention relates to the compounds of formula (I) in which:
• R 2a , R3a and R4a identical or different, each independently represent:
• R 2 , R and R 4 each independently represent a (C ⁇ -C 4 ) alkyl group
• R ⁇ , R 2b , R 3b and R ⁇ identical or different, each independently represent:
• a group -N CHR 5 in which R5 represents a (C ⁇ -C 4 ) alkyl, pyridyl or phenyl group,
• R 6 represents a hydrogen atom, a (C ⁇ -C 4 ) alkyl, tri (C ⁇ -C) alkylsilyl phenyl group, or a group of formula:
• R 6 ' represents a hydrogen atom or a phenyl optionally substituted in para by a (C ⁇ -C 6 ) alkyl group
• R 7 represents a hydrogen atom
• R 8 represents a hydrogen atom or a group -C (O) R 5 with R 5 chosen from a group (C ⁇ -C 4 ) alkyl, pyridyl or phenyl
• R 5 chosen from a group (C ⁇ -C 4 ) alkyl, pyridyl or phenyl
• at least one of the substituents Ri b , R 2b , R 3b or R 4b is different hydrogen or tert-butyl; as well as their salts, solvates and hydrates.
• the present invention relates to the compounds of formula (I) in which:
• R 2a , R3a and R a identical or different, each independently represent:
• R 2 , R and R 4 each independently represent a (C ⁇ -C 4 ) alkyl group
• - Ri b , R2 b> R3b and R 4b identical or different, each independently represent:
• R 6 represents a hydrogen atom or a phenyl group, or a group of formula:
• R 6 ' represents a hydrogen atom or a phenyl optionally substituted in para by a (C ⁇ -C) alkyl group
• R 7 represents a hydrogen atom
• R 8 represents a hydrogen atom or a benzoyl group
• R 7 represents a hydrogen atom
• R 8 represents a hydrogen atom or a benzoyl group
• at least one of the substituents Rib, R 2b , 3b or R 4b is different from hydrogen or from the tez-t-butyl group; as well as their salts, solvates and hydrates.
• R 2b , R 3 b and R 4b represents a nitro group
• -N CHR 5 or -NR 7 R 8 , in which R 7 represents a hydrogen atom and R 8 represents a hydrogen atom or a group - C (O) R 5 , with R 5 chosen from a group (C ⁇ -C 4 ) alkyl, pyridyl or phenyl, as well as their salts, solvates or hydrates, constitute a further aspect of the invention.
• the subject of the present invention is also the thiacalix [4] renes of formula (la):
• R ⁇ a , R2a, Rib and R 2 b are as defined above; as well as their salts, solvates or hydrates.
• the thiacalix [4] arenes of formula (la) in which R ) a represents a hydrogen atom or a (C ⁇ -C ⁇ 2 ) alkyl or (C ⁇ -C ⁇ 2 ) alkenyl group and R 2a represents a hydrogen atom or a group (C ⁇ -C ⁇ 2 ) alkyl, (C ⁇ -C ⁇ 2 ) alkenyl, -SO 2 -R ⁇ or -SiR 2 R3R 4 ; Ri, R 2 , R3 and i being as defined above; as well as their salts, solvates and hydrates.
• the invention relates to the thiacalix [4] arenas of formula (Ib):
• R] a , R 2a and Rib are as defined above for (I) and (la); as well as their salts, solvates and hydrates.
• the subject of the invention is the thiacalix [4] arene derivatives of formula (Ie): in which R ⁇ a and R ⁇ are as defined above for (I) and (la); as well as their salts, solvates and hydrates.
• the present invention also relates to the thiacalix [4] arenas chosen from:
• 26,28-dihydroxythiacalix [4] arene, - 5,17-Diiodo-25,26,27,28-tetrahydroxythiacalix [4] arene, - 5,17-Dibromo-25,26,27,28-tetrahydroxythiacalix [4] arene,
• the different conformers of the compounds of formulas (I), (la), (Ib) and (le), namely cone conformation, partial cone, 1,2-altemé, 1,3-alterné (Tetrahedron 1999, 40, 373 -376) are an integral part of the invention.
• the thiacalix [4] arenes according to the present invention can be prepared according to methods analogous to those used, for example for the synthesis of the 25,26,27,28-tetrahydroxythiacalix [4] arene described in particular in Tetrahedron Letters , 1998, 39, 2311-2314, or for the synthesis of 5,11,17,23 -tetra- (tert-butyl) -25,26,27,28-tetrahydroxythiacalix [4] arene; or else, the compounds according to the invention can be obtained by total or partial functionalization of these known compounds used as starting materials.
• the compounds of formula (I) may contain precursor groups of other functions which will be generated subsequently in one or more other stages.
• the compounds of formula (I) in which R ⁇ a , R 2a , R 3a and / or R 4a are different from hydrogen can be obtained from the corresponding compounds in which the said group (s) R] a , R 2a , R 3a and / or R 4a are a hydrogen atom by total or partial functionalization of the hydroxyl function in the presence of a base by the action respectively of a halogen derivative of type Hal-R ' ⁇ a , Hal-R' a , Hal-R ' 3a and / or Hal-R' 4a in which Hal represents a halogen atom, for example a chlorine or iodine atom and R' ⁇ a , R '2a, * 3a and R' 4a respectively represent Rj a , R a , R 3a or R 4a or a precursor group of the latter.
• the compounds (I) in which Rib, R 2 b, R3b and / or ib represent a group different from hydrogen are, for example, fully or partially functionalized, starting from the corresponding thiacalixarene in which the said compound (s) ) group (s) Ri b , R 2b , R 3b and / or i b represent hydrogen or a precursor group of the desired function.
• alkynyl derivative is of the -C ⁇ CR 6 type in which R 6 represents a (C ⁇ -C 4 ) alkyl, tri (C ⁇ -C 4 ) alkylsilyl, phenyl or a group of formula:
• R 6 ' is as defined above for (I), starting from the corresponding compound (I) in which the said group (s) Rib, R2 b , R 3b , and / or R 4b represent a halogen atom, by the action of the HC ⁇ CR 6 derivative, R 6 being as defined above, in the presence of tri- or diethylamine and a palladium catalyst, according to the Sonogashira reaction, as described for example, in Tetrahedron Letters, 1975, 50, 4467-4470 or EUT. J. Org. Chem. 2000, 3679-3681;
• the subject of the present invention is a process for preparing the compounds of formula (I) in which at least one of the substituents Rib, R2b, R3b or
• R 4b represents a nitro group
• -N CHR 5 or -NR 7 R 8 , in which R 7 represents a hydrogen atom and R 8 represents a hydrogen atom or a group -C (O) R 5 with R 5 chosen from a group (C ⁇ -C) alkyl, pyridyl or phenyl, characterized in that: a) if Rib, R2 b> R3b and / or R 4 b represent a nitro group, the compound (I) is obtained by nitration of the corresponding thiacalix [4] arene in which the said group (s) Ri b , R 2b , R 3b and / or R represent a hydrogen atom, by the action of nitrogen dioxide or tetroxide dinitrogen in the presence of an ethereal solvent; b) if Rib, R 2 b, R3b and / or R 4 b represent an amino group, the compound (I) is obtained by reduction of the corresponding compound (
• dimerized nitrogen dioxide also called dinitrogen tetroxide.
• This nitrogen dioxide forms a complex with the ether used which can be for example di, tri or tetraglyme or a crown ether.
• nitrogen or one prepared in situ will be used, for example by the action of a nitrate of the alkali metal nitrate type such as potassium nitrate in the presence a Lewis acid such as aluminum trichloride.
• the nitrogen dioxide / ether complex can be synthesized in situ or previously prepared by bubbling nitrogen dioxide in the cold ethereal solvent.
• the functional groups optionally present in the compounds of formula (I), (la), (Ib) (le) and in the reaction intermediates, can be protected, either permanently or temporarily, by protecting groups which ensure a unique synthesis of the expected compounds.
• the protection and deprotection reactions are carried out according to techniques well known to those skilled in the art. Those skilled in the art will be able to choose the appropriate protecting groups.
• the compounds (I) are isolated and purified, by means of conventional separation techniques: it is possible, for example, to use recrystallizations or else conventional techniques of chromatography on chiral or non-chiral phase.
• the subject of the present invention is also the complexes (II) of the compounds of formula (I), (la), (Ib) and (le) with a metal and in particular a transition metal with varying degrees of oxidation.
• a metal in particular a transition metal with varying degrees of oxidation.
• transition metal mention may, for example, be made of: copper, palladium, mercury, gold and more preferably, silver, zinc, platinum or lead.
• complexes (II) are obtained according to techniques well known to those skilled in the art, for example, by adding a metal salt to the thiacalix [4] arene of formula (I) in solution in an appropriate organic solvent, by for example, tetrahydrofuran, chloroform or pyridine.
• the complexes according to the invention are, for example, capable of being obtained by reaction of a thiacalix [4] arene of formula (I) with a metal derivative of the type: AgSO 3 CF 3 , zinc chloride (II), copper (II) chloride, Trans- [PtCl (PEt 3 ) 2 (C ⁇ C- phenyl)] or Trans- ⁇ PtCl (PEt 3 ) 2 [C ⁇ C- (4-pentylphenyl)] ⁇ or another platinum complex comprising another phosphine of trialkylphosphine type and / or a phenyl group differently substituted in position 4 with another alkyl group, this list being in no way limiting.
• the compounds of formula (I) as well as their metal complexes (II), according to the invention have third-order non-linear optical properties.
• the derivatives according to the invention are therefore particularly advantageous and can be used in particular as optical limiters. They may be used for the manufacture of materials having optical limiter properties. They can be incorporated into glass-type matrices, using, for example, the sol-gel process (CJ Brinker, GW Scherer, Sol-Gel Science. The Physics and Chemistry of Sol-Gel Processing, Académie Press, 1990 and LC Klein , Sol-Gel Optics: Processing and Applications, Kluwer Académie Publishers, 1994) to develop protective materials against lasers.
• sol-gel process CJ Brinker, GW Scherer, Sol-Gel Science. The Physics and Chemistry of Sol-Gel Processing, Académie Press, 1990 and LC Klein , Sol-Gel Optics: Processing and Applications, Kluwer Académie Publishers, 1994
• the complexes (II) according to the invention with zinc, copper or nickel are colored compounds which have advantageous coloring properties as a function of the temperature.
• the compound IL 5 (example 5B) changes from the purple color to a deep burgundy color as soon as the temperature reaches 25 ° C. This transformation is reversible and the compound regains its initial coloration on cooling. The compound is stable over time and can undergo a large amount of color change cycles.
• DSC820 Mettler Toledo Differential Calorimetric Analysis
• thermochromic materials They can therefore be used for the manufacture of thermochromic materials.
• the thiacalix [4] arenas (I) according to the invention can be used for the treatment of water, in particular they can make it possible to selectively extract organic compounds (Chemistry Letters, 1999, 777) or cations (Tetrahedron Letters 1998, 39, 7559 and 2001, 42, 1021).
• NMR nuclear magnetic resonance
• 0.5 g of 5, ll, 17.23-tetra (tert-butyl) -25,26,27,28-tetrahydroxythiacalix [4] arene are dissolved in 40 ml of dichloromethane.
• 0.1 g of imidazole and 1.255 g of tert-butyldimethylsilane chloride are added to the solution.
• the solution is stirred for about 24 hours at room temperature, then acidified with 40 ml of 1M hydrochloric acid.
• the organic phase is washed with 30 ml of saturated solution in sodium chloride and twice 30 ml of water then dried over sodium sulfate.
• the organic phase is concentrated, then precipitated with methanol.
• reaction mixture is heated at 40 ° C for 24 hours, then treated with HCl (10%) and extracted with 40 ml of ethyl acetate, the organic phase is washed with water (2 x 30 ml) then dried over Na 2 SO 4 . Finally the product is purified by column chromatography (8: hexane / 2 CHC1 3 ).
• Trans- [PtCl (PEt 3 ) 2 (C ⁇ C-phenyl)] is dissolved in a mixture of 1 toluene / 1 diethylamine.
• a solution of 0.028 g of 5, ll, 17.23-Tetraethynyl-25,26,27,28-tetrapropoxythiacalix [4] arene (compound 22.1) in 10 ml of toluene.
• the reaction mixture is stirred at room temperature for 24 hours, evaporated to dryness and then taken up in dichloromethane.

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